Linalool homologues



United States Patent 3,296,080 LINALOOL HOMOLOGUES Walter C. Meuly, New Brunswick, and Petko S. Gradefi', Franklin Township,Somerset County, N.J., asslgnors 3,296,080 Patented Jan. 3, 1967 where R is a lower alkyl group other than methyl and containing from two to six carbon atoms and R is H or a lower alkyl group containing one to five carbon atoms. R and R may form together a trimethylene or 5 tetramethylene group. If R is greater than methyl, R @oili Inc. New York N'Y'? a col-Donne of New may be methyl. The 4-position of the carbinol may be No Drawing. Filed Aug. 8, 1963, Ser. No. 300,907 subsumed by two methyl groups in place of H and 2- 7 a 12 Claims. (Cl.,167-94) These tertiary carbinols can be prepared conveniently V from a group of novel ketones disclosed in our copending This invention rel-ates to a number of novel composiapplication Serial No. 241036, now abandoned, examples tions of matter, being valuable odoriferous materials as 33, 62 to 73, by reacting said ketones with acetylene to such, or key intermediates. They, have utility in the form ethynyl carbinols, followed by selective hydrogenaperfume, cosmetic, or flavor industries. They are espetion to vinyl-carbinols or by reacting said ketones with cially valuable as odor-imparting agents in perfume comvinyl magnesium halide to yield directly the vinyl carpositions. Some of them are distinctly novel odors of 15 binols, according to reactionl great potential value, others are related to known odoriferous material but all have novel nuances, great intensity andlastin ower.

In the of perfumery, the terpenic alcohol linalool, (1) I 5 CH3 & CH3 the terpenic aldehyde citral and the ketonic ionones have H0 4 long been known and used as valuable ingredients. Their k/ w HG CH CH2 importance has led to their synthetic manufacture to re- H2O 0:0 H2O place natural oils of foreign origin. In addition many OH homologous products have been prepared by substituting I 1 R1 alkyl groups for hydrogen in various, positions of the 1 R2 linalool citral land ionone molecule. Ketones Vinyl-Oarbinols OH (A) 93 i 1 I HG 7 OH=CHg Where R and R have the same meanings as above. As is pointed out in said copending application Serial H20 5 4 3 G OH No. 241036, the ketones are formed in a very economical CH3 manner which makes the products of the present applica- Ht .tion available at a low cost which further enhances their Lillal'ool value as erfumery chemicals. The ketones of application In the case of linalool the prior art reveals homologs with i l 241036 re Obtained as a mixture of two lk l b tit ti i iti 1, 2, 5, 6, 8 and to a Limited isomers, if derived from an unsymmetrical starting ketone degree in position 4. Winter et a1. Helv. 30 (1947) 2213, with ahydrogen atom in each of the two alpha positions. describes a compound of this type where R and R are While it is usually possible to separate the isomers by methyl groups. No compounds are known, however, in 40 fractional distillation it has been found that the mixed which the alkyl gTOuP in the 3 PQSi'Ii011 is other than ketones lead to a mixture of two isomeric vinyl carbinols y 0111' novel gnsawrated fq 1' characterized which possess excellent odor characteristics, richer and by novel alkyl Subsmtuents 1n P 3 and/or closer to natural products (which are normally mixtures and many of F w prodlfcts Possess unusually deslrable of related chemicals). While we describe in several odor propemes .Whlch brmgs' them closer valuable examples below the properties of the mixed vinyl carbinols natural oils such i lavendey bergamot geramum' ed (which are obtained in definite ratios from the cor-relnacomprehensive embogimeintthese i i i sponding ketone mixtures of Serial No. 241036) it is alcohols are ternary m0 cqi'respon. mg 0 e understood that the individual isomers that make up the general formula mixtures are also withm the scope of this lnvention. (B) 5 The invention is further disclosed in the following HG examples, which are illustrative but not limitative thereof. For greater convenience in tracing the novel linalool H20 3 homologs described in the examples below, they are listed 4 in Table I along with the number of the example and the OH significance of the substituents R and R in the general 2 Formula B, above.

. TABLE I Example N Novel Linalool Homolog R2 CH3. gHgcHzoHncHz.

(CH3) 20H. H

Isobutyl ((511101 4 in position. H

Example 1.154 g. (1.0 mol) 4,7-dimethytl-6-octen-3- one prepared according to Serial No. 241036 were added with agitation during a five hour period into a solution of 1.2 mol vinyl magnesium halide in tetrahydrofu-ran. Thereaction mixture was kept at 1520 C. during the addition and held at least another hour after the end of the addition. Then the reaction mixture was poured simultaneously with a 15% ice cold aqueous solution of 70 g. acetic acid, into a large cooled flask under eflicient stirring. The resulting solution separated in two layers. The top layer containing all the product and most of the tetrahydrofuran was distilled at atmospheric pressure or slight vacuum, in order to remove the solvent. On' fractionation the crude material yielded 155 g. pure 4,7- dimethyl-3-ethyl-1,6-octadien-3-ol in the form of a colorless liquid b :69 C., N =1.4700, purity by Vapor Phase Chromatography 99%100%. This is a yield of 85% of theory. The product has a very lasting odor related to linalool but with a more flowery character and a definite lily of the valley note. It is much more useful in the perfuming of toilet soap than is linalool.

Example 2.2 (3-methyl-2-butenyl)-cyclohexanone (166 g.) was treated with vinyl magnesium halide and worked up as described in Example 1. On fractionation 165 g. of 1-vinyl-2-(3-methyl-2 buten-1-yl)-cyclohexanol (cis and trans isomers) was obtained. b :8589 C., N =1.4935-1.4939. Purity by V.P.C. 99100%, yield 85% of theory. The odoris fresh, leafy with a very natural linden type note.

Example 3a.7-methyl-6-octen-3-one is obtained according to Example 33 of Serial No. 241036 by careful fractionation of the mixture of 3,6-dimethyl-5-hepten-2- one and 7-methyl-6-octen-3-one. The latter boils about 4 C. higher than the former, is found in the later cuts of the fractionation and has the following constants: b :63 C.; N =1.4452. The lower boiling 3,6-dimethyl- S-hepten-Z-one has the constants b 59 C., N =1.4424. 140 g. (1.0 mol) 7-methyl-6-octen-3-one were reacted with vinyl magnesium halide as in Example 1 and the reaction mass was worked up in the same manner. There were obtained after fractionation .140 g. 7-methyl-3-ethyl- 1,6-octadien-3-ol or 83% of theory. The pmity by V.P.C. is 99%. The product is a colorless mobile liquid, b :65 C.; N =1.4647. The odor is a powerful and fragrant linalool type, more floral and richer than linalool and with a note of mu'gwet. It is much more lasting than linalool and lends smoothness and coherence to perfume compositions. It is much richer and natural than the knownhomolog, corresponding to R =CH R =CH in Formula B, above.

Example 3b.-A mixture of 7-methyl-6-octen-3-one and 3,6-dimethy1'5-hepten-2-one is reacted with vinyl magnesium halide as in Example 3a, and a mixture of isomers comprising 7 methyl 3 ethyl-1,6-octadien- 3-01 and 3,4,7 trimethyl 1,6-octadien-3-ol is obtained. This mixture has the constants: b :61 C.; N =1.4676,

' and the purity by V.P.C. is 99.5%. The odor of these mixed isomers is slightly sweeter and less flowing than the single isomer product of Example 3a, but it has the same advantages over linalool. The acetic acid ester of the mixture is a colorless liquid with b :62 C.; N =1.4581, purity by saponification or V.P.C.:97- 98%, the remainder being unchanged alcohol. This ester has a fresh flowery bergamot character much more than linalyl acetate. Used in perfuming soap, it is much more lasting and stable than linalyl acetate and resembles more natural bergamot oil.

Example 4.-A mixture of 3,3,6-trimethyl-5-hepten-2- one with 2,7-dimethyl-6-octen-3-one (154 g.) was reacted and worked up as described in Example 1. On fractionation, a mixture of 3,4,4,7-tetramethyl-1,6-octadien-3-ol with 7 methyl 3 isopropyl-1,6-octadien-3-ol was obtained with the constants b :64-66 C.;

4 purity by V.P.C. is 100%. The product has a strong geranium oil character and. it is excellent as a soap perfume.

Example 5 .--385 g. of 3-ethyl-6-methyl-5-hepten-2-one with 8-methyl-7-nonen-4-one was reacted and worked up as described in Example 1. On fractionation, 294 g. product was obtained with the constants b :6870 C.; N :1.4677-1.4680. Purity by V.P.C. is -97% identified as a mixture of 3,7 dimethyl 4 ethyl-1,6- octadien-3-ol with 7 methyl 3 propyl-1,6-octadien- 3-01, possessing a sweet and lasting linalool character.

Example 6.232 g. mixture of 6-methyl-3-isopropyl- 5-hepten-2-one with 2,8-dimethyl-7-none-4-one was reacted and worked up as described in Example 1. On fractionation 208 g. mixture of 3,7-dimethyl-4-isopropyl- 1,6-octadien-3-ol with 3-isobutyl-7-methyl-1,6-olctadien- 3-01 was obtained. The constants were b :70 72 C.; N =1.4662-1.4666, purity by V.P.C. 98100%. It has a fruity linalool note.

Example 7.365 g. mixture of 6,9-dimethyl-8-decen- 5-one with 4-propyl-7-methyl-6-octen-3-one was reacted and worked up as described in Example 1. On fractionation, 335 g. of product was obtained, with constants b :6570 C.; N =1.46941.4700, purity by V.P.C. 100%, identified as a mixture of 4,7dimethyl-3-butyl-1,6- octadien-3-ol with 7 methyl 3 ethyl-4-propyl-l,6- octadien-3-ol. Yield 80% of theory. It has a fruity linalool odor of exceptional lasting power.

As the foregoing indicates, the present invention embraces a substantial number of new and useful chemical compounds either per se or as novel mixtures thereof, more especially, concomitantly produced isomers. These novel compositions of matter which are thus claimed per se include:

What is claimed is: 1. An unsaturated carbinol having the formula wherein separately R is an alkyl radical having froml to 6 carbon atoms and R is selected from the class consisting of hydrogen and alkyl radicals having from 1 to 5 carbon atoms, wherein R is a member of the group consisting of H and methyl, and when R is methyl, R is an alkyl radical having at least two carbon atoms and R is H, and when R and R are both methyl, R is methyl, and together R and R may form a bridging grouping selected from the group consisting of trimethylene and tetramethylene grouping.

. 4,7-dimethyl-3-ethyl-1,6-octadien-3-ol.

. 1-vinyl-2-(3-methyl-2-buten-l-yl)-cyclohexanol.

3,4,4,7-tetramethyll,6-octadien-3-ol.

. 3,7-dimethyl-4-ethyl-1,6-octadien-3-ol.

. 3,7-dimethyl-4-isopropyl-1,6-octadien-3-ol.

. 4,7-dimethyl-3-butyl-1,6-octadien-3-ol.

. 7-methyl-3-ethyl-4-propyl-1,6-octadien-3-o1.

As an odoriferous' composition, the isomeric mix.- ture consisting essentially of 3,4,4,7-tetramethyl-1,6- octadien-3-ol and 7-methyl-3-isopropyl-1,6-octadien-3-ol.

5 10. The odoriferous composition consisting essentially of 3,7 -dimethyl 4 ethyl-1,6-octadien-3-ol and 7-methy1- 3-propyl-1,6-octadien-3-ol.

11. The odoriferous composition consisting essentially of 3,7-dimethy1 4 isopropyl-1,6-octadien-3-ol and 3- 5 isobutyl-7-methyl-1,6-octadien-3-ol.

12. The odoriferous composition consisting essentially of 4,7-dimethyl-3-buty1-1,6octadien-3-ol and 7-methyl- 3-ethyl-4-propy1-1,6octadien-3-ol.

References Cited by the Examiner UNITED STATES PATENTS 6/1958 Normant 260-638 FOREIGN PATENTS 1,041,036 10/1958 Germany.

6 OTHER REFERENCES Curvigny et a1.: Bull. Soc. Chim. France, 1961, pp. 2423-33.

Mousseron et a1.: Oomptes Rendus de lAcademie des Sciences, vol. 247, pp. 1811-15, 1958.

Oppenlander et al.: J. Organic Chem., vol. 21, pp. 961-4, 1956.

Sutrzenegger et al.: 1". Organic Chem, vol. 28, pp. 920-2, 1963.

LEON ZITVER, Primary Examiner.

M. JACOB, T. G. DILLAHUNTY, Assistant Examiners. 

9. AS AN ODORIFEROUS COMPOSITION, THE ISOMERIC MIXTURE CONSISTING ESSENTIALLY OF 3,4,4,7-TETRAMETHYL-1,6-OCTADIEN-3-OL AND 7-METHYL-3-ISOPROPYL-1,6-OCTADIEN-3-OL. 